Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/02—Heterophasic composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/20—Recycled plastic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to polypropylene compositions suitable especially for automotive interior applications comprising mixed plastics polypropylene-based blends and inorganic fillers.
• compositions suitable for the automotive industry typically contain one or more heterophasic polypropylene copolymer(s), and/or random heterophasic copolymers, and conventionally some inorganic filler.
• Recycled polyolefin materials are conventionally cross-contaminated with non-polyolefin materials such as polyethylene terephthalate, polyamide, polystyrene or non-polymeric substances like wood, paper, glass or aluminum. Even worse, those post-consumer recycled polyolefin materials are readily available on a multi-ton scale but unfortunately have limited mechanical properties and frequently severe odor and/or emission problems.
• Non-published patent application EP 20 190 814.2 is related to polypropylene compositions for automotive applications which contain mixed plastics polypropylene-based blends originating from post-consumer recycled polyolefin streams and inorganic fillers, such as talc. These compositions show beneficial VOC properties and tiger stripes performance (MSE) so that these compositions can replace sophisticated heterophasic polypropylene copolymers in automotive applications. However, these compositions still show deficiencies in impact properties.
• MSE tiger stripes performance
• the present invention is based on the surprising finding that by carefully selecting the heterophasic propylene copolymer based virgin component in polypropylene based compositions, which contain mixed plastics polypropylene-based blends originating from post-consumer recycled polyolefin streams and inorganic fillers, such as talc, polypropylene based compositions with a superior balance of properties in regard of mechanical properties, heat stability and especially impact properties, such as in the instrumented puncture test.
• the compositions of the invention comprising mixed plastics polypropylene-based blends originating from post-consumer recycled polyolefin streams qualify for injection moulding applications, especially in the automotive area, such as interior automotive applications, and can replace sophisticated heterophasic polypropylene copolymers.
• the present invention relates to a composition suitable for automotive applications obtainable by blending at least components (A), (B) and (C)
• the present invention relates to an article, preferably a moulded article, more preferably a moulded automotive article comprising the composition as described above or below.
• the present invention relates to the use of the composition as described above or below for injection molding of articles, preferably automotive articles, more preferably automotive interior articles.
• Mixed plastics is defined as the presence of low amounts of compounds usually not found in virgin polypropylene blends such as polystyrenes, polyamides, polyesters, wood, paper, limonene, aldehydes, ketones, fatty acids, metals, and/or long term decomposition products of stabilizers.
• Virgin polypropylene blends denote blends as directly originating from the production process without intermediate use.
• mixed plastics can be equated with detectable amounts of polystyrene and/or polyamide-6 and/or limonene and/or fatty acids.
• Post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose.
• industrial waste refers to manufacturing scrap, respectively conversion scrap, which does not normally reach a consumer.
• a soluble fraction (SF) as obtained by CRYSTEX QC analysis having an intrinsic viscosity (iV(SF)) in the range from 0.9 to below 2.2 dl/g is typically found in material from recycling streams.
• the soluble fraction (SF) as obtained by CRYSTEX QC analysis has an intrinsic viscosity (iV(SF)) in the range from 0.9 to 2.1 dl/g.
• a polymer blend is a mixture of two or more polymeric components.
• the blend can be prepared by mixing the two or more polymeric components.
• a suitable mixing procedures known in the art is post-polymerization blending.
• Post-polymerization blending can be dry blending of polymeric components such as polymer powders and/or compounded polymer pellets or melt blending by melt mixing the polymeric components.
• Polypropylene-polyethylene blend refers to a composition containing both polypropylene and polyethylene including also polypropylene copolymers as well as polyethylene copolymers.
• the weight ratio polypropylene (A-1) to polyethylene (A-2) of 19:1 to 7:3 denotes the equivalent ratio as determined from calibration by iPP and HDPE and determination by IR spectroscopy.
• a polypropylene means a polymer being composed of units derived from propylene in an amount of more than 50 mol-%.
• a polyethylene means a polymer being composed of units derived from ethylene in an amount of more than 50 mol-%.
• elastomer denotes a natural or synthetic polymer having elastic properties.
• plastomer denotes a natural or synthetic polymer having which combines qualities of elastomers and plastics, such as rubber-like properties with the processing ability of plastic.
• An ethylene based plastomer means a plastomer being composed of units derived from ethylene in an amount of more than 50 mol%.
• the presence of a heterophasic nature can be easily determined by the number of glass transition points, like in dynamic mechanical analysis (DMA), and/or high resolution microscopy, like scanning electron microscopy (SEM), transmission electron microscopy (TEM) or atomic force microscopy (AFM).
• DMA dynamic mechanical analysis
• SEM scanning electron microscopy
• TEM transmission electron microscopy
• AFM atomic force microscopy
• XCS refers to the xylene cold soluble fraction (XCS wt.-%) determined at 25 °C according to ISO 16152.
• XCI refers to the xylene cold insoluble fraction (XCI wt.-%) determined at 25 °C according to ISO 16152.
• Reactor blend is a blend originating from the production in two or more reactors coupled in series or in a reactor having two or more reaction compartments.
• a reactor blend may alternatively result from blending in solution.
• a reactor blend stands in contrast to a compound as produced by melt extrusion.
• the present invention relates to a composition suitable for automotive applications obtainable by blending at least components (A), (B) and (C)
• composition suitable for automotive application according to the present invention is particularly suitable for injection molding of articles to be used in the interior of vehicles.
• the composition suitable for automotive application according to the present invention has one or more of the following characteristics:
• the composition has a melt flow rate MFR 2 (230°C, 2.16 kg, ISO 1133) of 20 to 60 g/10 min, preferably 21 to 50 g/10 min, more preferably 22 to 45 g/10 min.
• the composition can be characterized by CRYSTEX QC analysis.
• CRYSTEX QC analysis a crystalline fraction (CF) and a soluble fraction (SF) are obtained which can be quantified and analyzed in regard of the monomer and comonomer content as well as the intrinsic viscosity (iV).
• composition preferably shows one or all of the following properties in the CRYSTEX QC analysis:
• Said crystalline fraction (CF) preferably has one or more, preferably all of the following properties:
• Said soluble fraction (SF) preferably has one or more, preferably all of the following properties:
• the composition preferably comprises units derived from ethylene in an amount of from 10.0 to 30.0 wt.-%, more preferably from 12.5 to 27.5 wt.-%, still more preferably from 15.0 to 25.0 wt.-%.
• composition according to the invention preferably shows a superior balance of properties in regard of mechanical properties, heat stability and especially impact properties, such as in the instrumented puncture test.
• the composition preferably has a flexural modulus of from 1500 MPa to 2200 MPa, more preferably from 1600 MPa to 2000 MPa.
• the composition preferably has a Charpy Notched Impact Strength at 23 °C (CNIS at 23°C) of from 5.0 kJ/m 2 to 50.0 kJ/m 2 , more preferably from 5.5 to 45.0 kJ/m 2 .
• CNIS at 23°C Charpy Notched Impact Strength at 23 °C
• the composition has very good impact strength in the instrumented puncture test, especially at low temperatures:
• the composition preferably has a puncture energy, measured at 23°C, of from 12 to 65 J, more preferably from 14 to 60 J.
• the composition preferably has an energy at maximum force, measured at 23°C, of from 10 to 60 J, more preferably from 12 to 55 J.
• composition preferably has a puncture energy, measured at 0°C, of from 3 to 50 J, more preferably from 5 to 45 J.
• the composition preferably has an energy at maximum force, measured at 0°C, of from 3 to 50 J, more preferably from 5 to 45 J.
• composition preferably has a puncture energy, measured at -30°C, of from 3 to 50 J, more preferably from 5 to 45 J.
• the composition preferably has an energy at maximum force, measured at -30°C, of from 3 to 50 J, more preferably from 5 to 45 J.
• the composition preferably has a heat deflection temperature (ISO 75 B) of at least 95°C, more preferably from 96°C to 110°C.
• ISO 75 B heat deflection temperature
• composition preferably has a coefficient of linear thermal expansion (CLTE) of from 60 to 125 ⁇ m/mK, more preferably from 70 to 105 ⁇ m/mK.
• CLTE coefficient of linear thermal expansion
• composition of the invention mandatorily comprises components (A), (B) and (C) as described above or below in the accordantly described amounts.
• composition can optionally comprise additional polymeric components so that the composition may be obtainable by blending components (A), (B), (C) and one or more of the following components:
• the composition is obtainable by blending components (A), (B), (C) and (F), with (D) and (E) not being present,
• composition is obtainable by blending components (A), (B), (C), (E) and (F), with (D) not being present,
• composition is obtainable by blending components (A), (B), (C), (D) and (E), with (F) not being present,
• the mixed-plastics polypropylene blend (A) is suitably characterized by CRYSTEX QC analysis.
• CRYSTEX QC analysis a crystalline fraction (CF) and a soluble fraction (SF) are obtained which can be quantified and analyzed in regard of the monomer and comonomer content as well as the intrinsic viscosity (iV).
• the mixed-plastics polypropylene blend (A) shows the following properties in the CRYSTEX QC analysis:
• Said crystalline fraction (CF) has one or more, preferably all of the following properties:
• Said soluble fraction (SF) has one or more, preferably all of the following properties:
• the mixed-plastics polypropylene blend (A) comprises polypropylene and polyethylene.
• the weight ratio of polypropylene to polyethylene is preferably from 19:1 to 7:3.
• the mixed-plastics polypropylene blend (A) preferably comprises units derived from propylene in an amount of more than 50 mol-%.
• the mixed-plastics polypropylene blend (A) preferably comprises units derived from ethylene in an amount of from 2.5 to 15.0 wt.-%, more preferably from 4.0 to 12.5 wt.-%, still more preferably from 5.0 to 10.0 wt.-%.
• the mixed-plastics polypropylene blend (A) preferably has one or more, preferably all of the following properties:
• the mixed-plastics polypropylene blend according to the present invention is preferably present in the form of pellets. Pelletization contributes to the low amounts of volatile substances.
• the heterophasic polypropylene copolymer (B) comprises a matrix phase and an elastomer phase dispersed therein.
• the heterophasic propylene copolymer (B) is characterized by
• heterophasic propylene copolymer (B) has one or more, preferably all, of the following properties:
• heterophasic propylene copolymer (B) consists of propylene units and ethylene units.
• the content of units derived from propylene (C3) in the soluble fraction (SF) preferably adds up to 100 wt.-% with the content of units derived from ethylene (C2) in the soluble fraction (SF).
• the content of units derived from propylene (C3) in the soluble fraction (SF) is preferably 55 to 70 wt.-%, more preferably 60 to 68 wt.-%, still more preferably 62 to 67 wt.-%.
• the content of units derived from propylene (C3) in the crystalline fraction (CF) preferably adds up to 100 wt.-% with the content of units derived from ethylene (C2) in the crystalline fraction (CF).
• the content of units derived from propylene (C3) in the crystalline fraction (CF) is preferably 95.0 to 99.9 wt.-%, more preferably 96.0 to 99.8 wt.-%, still more preferably 97.0 to 99.5 wt.-%.
• the total content of units derived from propylene (C3) in the heterophasic propylene copolymer (B) is preferably 85.0 to 95.0 wt.-%, more preferably 88.0 to 94.0 wt.-%, still more preferably 90.0 to 93.0 wt.-%.
• Such heterophasic propylene copolymers are commercially available.
• the inorganic filler (C) is preferably talc.
• the inorganic filler, preferably talc, (C) preferably has a median particle size d 50 before compounding of 0.3 to 30.0 micrometers, more preferably 1.5 to 15.0 micrometers.
• the inorganic filler, preferably talc, (C) preferably has a top-cut particle size d 95 before compounding of 1.0 to 50.0 micrometers, preferably 5.0 to 35.0 micrometers.
• Such inorganic fillers are commercially available.
• Additives are commonly used in the composition according to the present invention.
• the additives are selected from one or more of antioxidant(s), UV stabilizer(s), slip agent(s), nucleating agent(s), pigment(s), lubricant(s), masterbatch polymer(s) and/or antifogging agents.
• Additives are usually present in the composition in an amount of from 0.01 to 4.0 wt.-%, preferably in an amount of 0.05 to 3.0 wt.-%, based on the total composition.
• the optional heterophasic polypropylene copolymer (D) comprises a matrix phase and an elastomer phase dispersed therein.
• the second heterophasic propylene copolymer (D), if present in the composition, preferably has a melt flow rate which is lower than the melt flow rate of the heterophasic propylene copolymer (B).
• the optional second heterophasic propylene copolymer (D) has a melt flow rate MFR 2 (230°C, 2.16 kg, ISO 1133) of 8 to 25 g/10min, preferably of 10 to 24 g/10min, more preferably of 12 to 23 g/10min.
• the optional second heterophasic propylene copolymer (D) has a soluble fraction (SF) content determined according to CRYSTEX QC analysis in the range from 12.5 to 30.0 wt.-%, preferably in the range from 14.0 to 27.0 wt.-%, more preferably in the range from 15.0 to 25.0 wt.-%.
• SF soluble fraction
• Said soluble fraction preferably has an intrinsic viscosity, iV(SF), as measured in decalin according to DIN ISO 1628/1 at 135°C, of 2.3 dl/g to 6.0 dl/g, preferably of 2.5 to 5.5 dl/g, more preferably of 2.6 to 4.5 dl/g.
• iV(SF) intrinsic viscosity
• the optional second heterophasic propylene copolymer (D) preferably has a crystalline fraction (CF) content determined according to CRYSTEX QC analysis in the range from 70.0 to 87.5 wt.-%, preferably in the range from 73.0 to 86.0 wt.-%, more preferably in the range from 75.0 to 85.0 wt,-%.
• CF crystalline fraction
• the optional second heterophasic propylene copolymer (D) has one or more, preferably all, of the following properties:
• the optional heterophasic propylene copolymer (D) consists of propylene units and ethylene units.
• the content of units derived from propylene (C3) in the soluble fraction (SF) preferably adds up to 100 wt.-% with the content of units derived from ethylene (C2) in the soluble fraction (SF).
• the content of units derived from propylene (C3) in the soluble fraction (SF) is preferably 55 to 70 wt.-%, more preferably 60 to 68 wt.-%, still more preferably 62 to 67 wt.-%.
• the content of units derived from propylene (C3) in the crystalline fraction (CF) preferably adds up to 100 wt.-% with the content of units derived from ethylene (C2) in the crystalline fraction (CF).
• the content of units derived from propylene (C3) in the crystalline fraction (CF) is preferably 92.5 to 99.5 wt.-%, more preferably 95.0 to 99.0 wt.-%, still more preferably 96.0 to 98.5 wt.-%.
• the total content of units derived from propylene (C3) in the heterophasic propylene copolymer (B) is preferably 85.0 to 95.0 wt.-%, more preferably 88.0 to 94.0 wt.-%, still more preferably 90.0 to 93.5 wt.-%.
• the optional second heterophasic polypropylene copolymer (D) preferably is nucleated, more preferably is nucleated by poly(vinylcyclohexane) as described e.g. in EP 2 960 279 B1 .
• Such heterophasic propylene copolymers are commercially available.
• High density polyethylene (E), particularly virgin high density polyethylene (E) may be added into the composition according to the present invention.
• High density polyethylene (E) contributes to the scratch resistance of the final composition. Due to the presence of high density polyethylene in blend (A), the amount of high density polyethylene (E) for a target scratch resistance may be reduced or may be omitted completely.
• the optional high density polyethylene (E) preferably has one or more, preferably all, of the following properties:
• Such high density polyethylenes are commercially available.
• the optional ethylene-based plastomer (F) is preferably copolymer of ethylene with comonomer units selected from alpha-olefins having from 3 to 12 carbon atoms, preferably from alpha-olefins having from 4 to 10 carbon atoms, most preferably from 1-octene.
• Ethylene- based plastomers are usually added for further improving the impact properties of the composition.
• the optional ethylene-based plastomer (F) preferably has one or more, preferably all, of the following properties:
• Such ethylene-based plastomer are commercially available under the tradename Engage, Exact, Queo, Tafmer or others.
• the present invention relates to an article, preferably a moulded article, more preferably a moulded automotive article comprising the composition as described above or below.
• the article is preferably used in the interior of vehicles.
• the article preferably shows a good surface quality.
• the article has a MSE surface quality of below 15, preferably below 14.
• the present invention relates to the use of the composition as described above or below for injection molding of articles, preferably automotive articles, more preferably automotive interior articles.
• the crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160°C, crystallization at 40°C and re-dissolution in 1,2,4-trichlorobenzene at 160°C.
• Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an integrated infrared detector (IR4) and for the determination of the intrinsic viscosity (iV) an online 2-capillary viscometer is used.
• the IR4 detector is a multiple wavelength detector measuring IR absorbance at two different bands (CH 3 stretching vibration (centred at app. 2960 cm -1 ) and the CH stretching vibration (2700-3000 cm -1 ) that are serving for the determination of the concentration and the Ethylene content in Ethylene-Propylene copolymers.
• the IR4 detector is calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13 C-NMR) and each at various concentrations, in the range of 2 and 13mg/ml.
• Amounts of Soluble Fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the "Xylene Cold Soluble" (XCS) quantity and respectively Xylene Cold Insoluble (XCI) fractions, determined according to standard gravimetric method as per ISO16152.
• XCS Xylene Cold Soluble
• XCI Xylene Cold Insoluble
• the samples to be analyzed are weighed out in concentrations of 10mg/ml to 20mg/ml. To avoid injecting possible gels and/or polymers which do not dissolve in TCB at 160°C, like PET and PA, the weighed out sample was packed into a stainless steel mesh MW 0,077/D 0,05mmm.
• the sample is dissolved at 160°C until complete dissolution is achieved, usually for 60 min, with constant stirring of 400rpm.
• the polymer solution is blanketed with the N2 atmosphere during dissolution.
• a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times.
• the whole sample is measured at high temperature, determining the iV [dl/g] and the C2 [wt.-%] of the PP composition.
• the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are measured (wt.-% SF, wt.-% C2, iV).
• Xylene cold soluble fraction (XCS) was determined at 25 °C according ISO 16152; first edition; 2005-07-01. The part which remains insoluble is the xylene cold insoluble (XCI) fraction.
• Intrinsic viscosity was measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 °C).
• the flexural modulus was determined according to ISO 178 at a test speed of 2 mm/min and a force of 100 N, whereby the length of the span between the supports was 64 mm, on test specimens having a dimension of 80 x 10 x 4 mm 3 (length x width x thickness) prepared by injection moulding according to EN ISO 1873-2.
• Instrumented puncture test was performed on 60 x 60 x 3 mm 3 injection-molded plaques at 23°C, 0°C and -30°C according to ISO6603-2:2000. The measurement was done after 96 h conditioning time at 23 °C of the specimen.
• IR infrared
• Quantitative IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 25x25 mm square films of 300 ⁇ m thickness prepared by compression moulding at 180 - 210°C and 4 - 6 MPa. For samples with very high ethylene contents (>50 mol%) 100 ⁇ m thick films were used. Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-500 cm -1 , an aperture of 6 mm, a spectral resolution of 2 cm -1 , 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 64 and Blackmann-Harris 3-term apodisation.
• Quantitative analysis was undertaken using the total area of the CH 2 rocking deformations at 730 and 720 cm -1 (A Q ) corresponding to (CH 2 ) >2 structural units (integration method G, limits 762 and 694 cm -1 ).
• the quantitative band was normalised to the area of the CH band at 4323 cm -1 (A R ) corresponding to CH structural units (integration method G, limits 4650, 4007 cm -1 ).
• the ethylene content in units of weight percent was then predicted from the normalised absorption (A Q / A R ) using a quadratic calibration curve.
• the calibration curve having previously been constructed by ordinary least squares (OLS) regression of the normalised absorptions and primary comonomer contents measured on the calibration set.
• Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme ( Zhou, Z., et al. J. Mag. Reson. 187 (2007) 225 , and in Busico, V., et al, Macromol. Rapid Commun. 2007, 28, 1128 ).
• a total of 6144 (6k) transients were acquired per spectra.
• Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent.
• Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
• E 0.5(I H +I G + 0.5(I C + I D )) using the same notation used in the article of Wang et. al.
• Equations used for absolute propylene content were not modified.
• the comonomer content was determined from the spectrum from the wave number range of from 1430 to 1100 cm -1 .
• the absorbance was measured as the height of the peak by selecting the so-called short or long base line or both.
• the short base line was drawn in about 1410 - 1320 cm -1 through the minimum points and the long base line about between 1410 and 1220 cm -1 . Calibrations needed to be done specifically for each base line type. Also, the comonomer content of the unknown sample was within the range of the comonomer contents of the calibration samples.
• melt flow rates were measured with a load of 2.16 kg (MFR 2 ) at 230 °C (polypropylene based materials) or at 190 °C (polyethylene based materials).
• the melt flow rate is that quantity of polymer in grams which the test apparatus standardized to ISO 1133 extrudes within 10 minutes at a temperature of 230 °C (or 190°C) under a load of 2.16 kg.
• Density was measured according to ISO 1183-187. Sample preparation was done by compression molding in accordance with ISO 1872-2:2007.
• the HDT was determined on injection molded test specimens of 80x10x4 mm 3 prepared according to ISO 1873-2 and stored at +23°C for at least 96 hours prior to measurement. The test was performed on flatwise supported specimens according to ISO 75, condition B, with a nominal surface stress of 0.45 MPa.
• CLTE coefficient of linear thermal expansion
• This method consists of two aspects:
• plaques 440 ⁇ 148 ⁇ 2.8 mm 3 with grain VW K50 and a filmgate of 1.4 mm were used and were produced with different filling times of 1.5, 3 and 6 sec respectively.
• TEAL triethyl-aluminium
• donor D dicyclopentadienyl-dimethoxysilana
• HECO 1, HECO 2 and HECO 3 were made in a Borstar PP pilot plant with prepolymerization / loop reactor / gas phase reactor 1 / gas phase reactor 2 / gas phase reactor 3 configuration followed by a pelletization step.
• Table 1 Preparation of HECO 1, HECO 2 and HECO 3 HECO 1 HECO 2 HECO 3 Catalyst As described above, nucleated As described above, nucleated As described above, non-nucleated Donor D D D D Prepoly Co/ED mol/mol 7.0 20 20 Co/Ti mol/mol 390 250 250 Temperature °C 28 21 20 Residence time min 0.27 0.33 0.33 Loop Temperature °C 75 80 70 Pressure kPa 5500 5455 5380 Split wt.-% 44 51 40 H2/C3 mol/kmol 36.7 6.40 12.0 MFR g/10 min 511 42 100 GPR1 Temperature °C 80 80 85 Pressure kPa 2100 2600 2670 Split wt.-% 38 30 45 H2/C3
• heterophasic copolymers HECO 1, HECO 2 and HECO 3 were compounded in a co-rotating twin-screw extruder Coperion ZSK 47 at 220°C with 0.15 wt.-% antioxidant (Irganox B215FF from BASF AG, Germany; this is a 1:2-mixture of Pentaerythrityl-tetrakis(3-(3',5'-di-tert. butyl-4-hydroxyphenyl)-propionate, CAS-no. 6683-19-8, and Tris (2,4-di-t-butylphenyl) phosphite, CAS-no.
• Table 3 shows the properties of the polypropylene / polyethylene blends (A) as used for the evaluation. As these compositions come from a mechanical recycling process, the properties are indicated as ranges. Table 3: Properties of Polypropylene / Polyethylene Blends Mixtures (Blend A) Blend A PP / PE ratio 11 : 1 C2 (Blend A, total), wt.-% 6.6-8.3 Recycling origin Yes, households limonene > 0.1 ppm MFR 2 (230°C, ISO1133), g/10min 12.0-15.0 CF (CRYSTEX), wt% 89.7-90.3 iV (CF), dl/g 1.80 C2 (CF), wt% 5.7-7.4 SF (CRYSTEX), wt% 9.7-10.3 iV (SF), dl/g 1.20-1.65 C2 (SF), wt% 27.0-29.0
• HDPE 1 was the commercial grade MB5568 of Borealis AG, Austria, having a density of 955 kg/m 3 (ISO 1183), MFR 2 (2.16 kg, 190°C, ISO1133) of 0.8 g/10min and a tensile modulus of 1000 MPa (ISO 527-2).
• HDPE 2 was the commercial grade MB7541 of Borealis AG, Austria, having a density of 954 kg/m 3 (ISO 1183), MFR 2 (2.16 kg, 190°C, ISO1133) of 4 g/10min and a tensile modulus of 850 MPa (ISO 527-2).
• Plastomer 1 was Engage 8842, being an ethylene-1-octene plastomer with a density of 857 kg/m 3 and a MFR 2 (2.16 kg, 190°C, ISO1133) of 1.0 g/10min, commercially available from DOW, Inc, USA.
• Plastomer 2 was Engage 8180, being an ethylene-1-octene plastomer with a density of 863 kg/m 3 and a MFR 2 (2.16 kg, 190°C, ISO1133) of 0.5 g/10min, commercially available from DOW, Inc, USA.
• Talc 1 was Luzenac HAR T84 with a d 50 of 2.0 ⁇ m and a d 95 of 10.0 ⁇ m (Sedigraph measurement), commercially available from IMERYS, France.
• Talc 2 was Jetfine 3CA with a d 50 of 1.2 ⁇ m and a d 95 of 3.3 ⁇ m (Sedigraph measurement), commercially available from IMERYS, France.
• compositions were compounded in a Coperion ZSK40 twin-screw extruder at 220°C using the polymers and talc together with antioxidants, UV-stabilizers, slip agents, nucleating agents, carbon black masterbatch, calcium stearate, antifogging agent.
• antioxidants UV-stabilizers
• slip agents slip agents
• nucleating agents carbon black masterbatch
• calcium stearate calcium stearate
• antifogging agent The compositions of the examples are shown in Table 4.
• Table 4 Compositions of the examples CE1 CE2 CE3 IE1 IE2 IE3 IE4 IE5 HECO1, wt.-% - - 19.0 19.0 34.4 47.6 47.6 HECO2, wt.-% 40.95 28.45 15.95 19.9 20.4 - - - HECO3, wt.-% 39.95 27.45 14.95 - - - - - Blend A, wt.-% - 25.0 50.0 40.0 40.0 40.0 20.0 20.0 Plastomer 1, wt.-% - - - - - - 5.0 - 15.0 Plastomer 2, wt.-% - - - - - - - 15.0 - HDPE1, wt.-% - - - 7.0 7.0 - - HDPE2, wt.-% 7.0 7.0 - - - - Talc 1, wt.-% - - - - -
• Table 5 shows the properties of the examples. Table 5: Properties of the examples CE1 CE2 CE3 IE1 IE2 IE3 IE4 IE5 MFR 2 , g/10 min 22 18 14 23 23 26 24 26 C2 (Comp), wt% 22.0 16.0 12.2 16.3 16.3 19.7 23.0 22.0 iV (Comp), dl/g 1.88 1.74 1.77 1.63 1.63 1.53 1.59 1.56 CF (CRYSTEX), wt% 79 84 79 84 85 79 67 67 C2 (CF), wt% 14.2 13.0 13.8 13.5 13.5 13.8 4.8 5.25 iV (CF), dl/g 1.42 1.69 1.46 1.56 1.56 1.44 1.28 1.31 SF (CRYSTEX), wt% 21 16 21 16 15 21 33 33 C2 (SF), wt% 39.8 36.0 33.5 32.6 32.6 43.5 59.0 57.0 iV (SF), dl/g 1.42 1.93 1.78 2.
• n.m. n.m. 25.0 13.0 Puncture energy, -30°C, J n.m. n.m. n.m. n.m. n.m. n.m. 27.0 15.0 HDT, °C 103 98 51 98 104 102 103 99 CLTE, +23/80°C, ⁇ m/mK, MD n.m. n.m. n.m. 98* 93* 91* 74 75 Tiger stripes, MSE 18 15 22 8 10 5 8 13 *the CLTE was evaluated from +23°C/85°C. The data can be compared to the one measured from +23/80°C n.m. not measured
• compositions according to the invention show improved impact properties in the instrumented puncture test, also at low temperatures and a good surface appearance in low Tiger stripes.
• the compositions of the invention thus qualify for automotive interior moulded articles thereby comprising mixed plastics polypropylene blends obtained from post-consumer waste in amounts of up to 40 wt.-%.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (6)

Applications Claiming Priority (1)

Publications (2)

Family

ID=76374897

Family Applications (1)

Country Status (6)

Citations (7)

• 2021
  • 2021-06-09 EP EP21178547.2A patent/EP4101889B1/de active Active
• 2022
  • 2022-06-07 KR KR1020247000369A patent/KR20240007718A/ko not_active Application Discontinuation
  • 2022-06-07 JP JP2023575363A patent/JP2024520750A/ja active Pending
  • 2022-06-07 CN CN202280040676.6A patent/CN117460774A/zh active Pending
  • 2022-06-07 WO PCT/EP2022/065331 patent/WO2022258576A1/en active Application Filing
  • 2022-06-07 BR BR112023025637A patent/BR112023025637A2/pt unknown

Patent Citations (7)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events